CN105732715A - Phosphorus-containing fluorine-containing synergic flame-retardant compound and preparation method thereof - Google Patents
Phosphorus-containing fluorine-containing synergic flame-retardant compound and preparation method thereof Download PDFInfo
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- CN105732715A CN105732715A CN201610053910.5A CN201610053910A CN105732715A CN 105732715 A CN105732715 A CN 105732715A CN 201610053910 A CN201610053910 A CN 201610053910A CN 105732715 A CN105732715 A CN 105732715A
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- fluorine
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 55
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 52
- 239000011737 fluorine Substances 0.000 title claims abstract description 52
- -1 flame-retardant compound Chemical class 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 title abstract description 11
- 239000011574 phosphorus Substances 0.000 title abstract description 11
- 230000002195 synergetic effect Effects 0.000 title abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 9
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 31
- 238000001291 vacuum drying Methods 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- ZDVRPKUWYQVVDX-UHFFFAOYSA-N 2-(trifluoromethyl)benzaldehyde Chemical compound FC(F)(F)C1=CC=CC=C1C=O ZDVRPKUWYQVVDX-UHFFFAOYSA-N 0.000 claims description 7
- 125000005842 heteroatom Chemical group 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 16
- 239000000126 substance Substances 0.000 abstract description 13
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical class N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract 2
- 238000004100 electronic packaging Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000005022 packaging material Substances 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000002390 rotary evaporation Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 13
- 239000003822 epoxy resin Substances 0.000 description 13
- 229920000647 polyepoxide Polymers 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 239000000843 powder Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- UGEJOEBBMPOJMT-UHFFFAOYSA-N 3-(trifluoromethyl)phenol Chemical compound OC1=CC=CC(C(F)(F)F)=C1 UGEJOEBBMPOJMT-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a phosphorus-containing fluorine-containing synergic flame-retardant compound and a preparation method thereof, relating to flame-retardant compounds. The preparation method comprises the following steps: carrying out reaction on a diamido compound and 5-bis(trifluoromethyl)benzaldehyde in a first solvent, carrying out rotary evaporation, and drying to obtain an intermediate containing carbon-nitrogen double bond; and carrying out reaction on the intermediate containing carbon-nitrogen double bond and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in a second solvent, precipitating the product with a precipitant, washing with the precipitant, and drying to obtain the phosphorus-containing fluorine-containing synergic flame-retardant compound. The compound simultaneously comprises the flame-retardant elements phosphorus and fluorine, and the phosphorus and fluorine have the synergic flame-retardant actions; and thus, the compound can be used as a flame retardant and has favorable flame-retardant effect. The introduced fluorine element can enhance the heat stability and chemical stability, lower the surface energy of the material and lower the dielectric constant and hydroscopic property of the material, thereby satisfying the required properties of the electronic packaging material. The compound contains two active groups, thereby being beneficial to enhancing the compatibility with the high-polymer material, improving the loss of the flame retardant and enhancing the flame retardancy.
Description
Technical field
The present invention relates to flame-retardant compound, especially relate to a kind of phosphorous fluorine-containing cooperative flame retardant compound and preparation method thereof.
Background technology
In recent years, along with the development of Electronic Encapsulating Technology, more and more higher to the performance requirement of epoxy resin, how to improve epoxy
Reduce its dielectric constant, hygroscopicity and the coefficient of expansion while the heat stability of resin, mechanical property and fire resistance, be urgently
Problem to be solved.Wherein, utilize multielement synergistic fire retardant that epoxy resin is modified, become and improve asphalt mixtures modified by epoxy resin lipid
Can a more promising direction.
Gu L et al. (Gu L, Chen G, Yao Y.Two novel phosphorus nitrogen-containing halogen-free
flame retardants of high performance for epoxy resin[J].Polymer Degradation and Stability,2014,
108:68-75.) utilize 4,4'-diaminodiphenyl ether, 4,4'-DADPS reacts with 3-methoxyl group-4 hydroxy benzaldehyde respectively,
Add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to be condensed, be prepared for two kinds of phosphorous nitrogenous halogen-free types fire-retardant
Agent, both fire retardants prepare through one kettle way, and preparation is convenient, and productivity is higher.This fire retardant is used for the fire-retardant of epoxy resin change
Property, phosphorus content only 0.73%～0.75% time material vertical combustion performance can reach V-0 level, and the vitrification of material turns
Temperature is greatly improved with carbon left.Although this fire retardant is effectively increased the fire resistance of material, but due to its dielectric constant
Do not improved with hygroscopicity, still cannot be met the requirement of electronic package material.
Ding J P et al. (Ding J P, Tao Z Q, Fan L, et al.Synthesis and properties of fluorinated
Biphenyl type epoxy resin [J] .Journal of applied polymer science, 2009,113 (3): 1429-1437.) utilize
Biphenyl dimethyl ether and m-trifluoromethyl phenol react and have obtained the phenolic resin that main chain is fluorine-containing, and further epoxidation obtains main chain and contains
The epoxy resin of fluorine.Utilize fluorine-containing phenolic resin that fluorine-containing epoxy resin is solidified, find compared with the most fluorine-containing system,
The heat stability of epoxy resin is improved significantly, and after tested, modified epoxy resin surface can reduce, contact angle test table
Bright modified epoxy has hydrophobic performance, and the specific insulation of this epoxy resin is up to 0.5～0.8 × 1017Ω cm, surface electricity
Resistance rate reaches 0.8～4.6 × 1016Ω, makes material list reveal good electric insulating quality.The introducing of fluorine element improves dielectric material
Can and hygroscopicity so that it is the application at electronic package material has a biggest prospect, but the introducing of only fluorine element, to material
The raising of fire resistance do not play the biggest effect.
Summary of the invention
Present invention aim at the shortcoming solving existing fire proofing, it is provided that a kind of phosphorous fluorine-containing cooperative flame retardant compound and preparation thereof
Method.
The structural formula of described phosphorous fluorine-containing cooperative flame retardant compound is as follows:
Wherein, R group can beOrDeng.
The preparation method of described phosphorous fluorine-containing cooperative flame retardant compound, comprises the steps:
1) by diamino compounds and 3, double (trifluoromethyl) benzaldehyde of 5-reacts in the first solvent, and rotation is steamed, and is contained after drying
The intermediate of carbon-to-nitrogen double bon, its structural formula is as follows:
Wherein, R group can beOrDeng；
In step 1) in, described first solvent is selected from methanol, ethanol, oxolane, dichloromethane, chloroform etc.
One；The proportioning of described diamino compounds and the first solvent can be 1g: (1～20) mL, wherein, and diaminourea chemical combination
Thing is calculated by mass, and the first solvent is in terms of volume；The condition of described reaction can react 2～10h at 25～90 DEG C；Described
The mol ratio of diamino compounds (trifluoromethyl) benzaldehyde double with 3,5-can be 1: (2～3)；Described being dried can use vacuum to do
Dry.
2) by step 1) intermediate containing carbon-to-nitrogen double bon prepared and 9,10-dihydro-9-oxy miscellaneous-10-phospho hetero phenanthrene-10-oxide be the
Reacting in two solvents, product precipitant precipitates, then washs with precipitant, the most i.e. obtains phosphorous fluorine-containing cooperative flame retardant
Compound.
In step 2) in, described containing carbon-to-nitrogen double bon intermediate, the mol ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
Can be 1: (2～3)；Described second solvent be selected from N,N-dimethylformamide, dimethyl sulfoxide, ethyl acetate, dichloromethane,
One in chloroform etc., the described proportioning containing carbon-to-nitrogen double bon intermediate and the second solvent can be 1g: (1～20) mL,
Wherein, the intermediate containing carbon-to-nitrogen double bon is calculated by mass, and the second solvent is in terms of volume；The condition of described reaction can be in 25～90 DEG C
Lower reaction 8～12h；Described precipitant is selected from the one in methanol, ethanol, normal hexane etc.；Washable 3 times of described washing；
Described being dried can use vacuum drying.
In order to combine the advantage of various ignition-proof element, improve macromolecular material dielectric constant, hygroscopicity and the performance such as fire-retardant, make ring
Epoxy resins can be preferably applied in electronic package material field, and the present invention has synthesized a kind of phosphorous fluorine-containing cooperative flame retardant compound,
And for the modification of epoxy resin, it is greatly improved ethoxyline resin antiflaming performance and dielectric constant etc. so that it is can be good at being applied to
Electronic package material field.
The invention has the beneficial effects as follows:
1, the compound of the present invention contains phosphorus and two kinds of ignition-proof elements of fluorine simultaneously, and both have the effect of cooperative flame retardant, can do and hinder
Combustion agent uses, good flame retardation effect；
2, the compound of the present invention introduces fluorine element, and the introducing of fluorine element can improve its heat stability and chemical stability, fluorine unit
The plain surface energy that can effectively reduce material, and then reduce dielectric constant and the hygroscopicity of material, meet the required of electronic package material
Performance；
3, the cooperative flame retardant compound of the present invention contains two active groups, is conducive to improving its compatibility with macromolecular material,
Improve the shortcoming that fire retardant runs off, promote fire resistance；
4, the present invention can be by changing the kind (i.e. changing the kind of diamino compounds) of R group in preparation process, preparation
Go out the fire retardant that variety classes and phosphorus, Oil repellent are different；
5, the compound of the present invention, preparation method is simple, and reaction condition is gentle, and conversion ratio is high, and product purity is high, is suitable for expanding
Produce.
Accompanying drawing explanation
Fig. 1 is the proton nmr spectra spectrogram in the embodiment of the present invention 1 containing carbon-to-nitrogen double bon intermediate.In FIG, abscissa is
Chemical shift (chemical shift (ppm)).
Fig. 2 is the proton nmr spectra spectrogram of phosphorous fluorine-containing cooperative flame retardant compound in the embodiment of the present invention 1.In fig. 2, horizontal
Coordinate is chemical shift (chemical shift (ppm)).
Fig. 3 is the nuclear magnetic resonance, NMR phosphorus spectrum spectrogram of phosphorous fluorine-containing cooperative flame retardant compound in the embodiment of the present invention 1.In figure 3, horizontal
Coordinate is chemical shift (chemical shift (ppm)).
Fig. 4 is the Enantiomeric excess spectrogram of phosphorous fluorine-containing cooperative flame retardant compound in the embodiment of the present invention 1.In the diagram, horizontal
Coordinate is chemical shift (chemical shift (ppm)).
Detailed description of the invention
Combine accompanying drawing below by way of specific embodiment technical scheme is described further.
Embodiment 1
Step 1, the synthesis of intermediate containing carbon-to-nitrogen double bon
First, by the 2 of 2g (3.86mmol), double [4-(4-amino-benzene oxygen) phenyl] 1,1,1,3,3, the 3-HFC-236fa and 1.86 of 2-
Double (trifluoromethyl) benzaldehyde of g (7.68mmol) 3,5-joins in the single port flask of 100mL, dissolves with 20mL methanol,
At 55 DEG C, stirring reaction 8h, is spin-dried for solvent with Rotary Evaporators, obtains pale yellow powder shape solid, i.e. after vacuum drying
For the intermediate containing carbon-to-nitrogen double bon.
The described sign containing carbon-to-nitrogen double bon intermediate as it is shown in figure 1, wherein chemical shift be that carbon nitrogen is double at 8.8ppm to 9.0ppm
The characteristic peak of C-H on key, is the characteristic peak of C-H on phenyl ring at six peaks of 7.0ppm to 8.7ppm.
Step 2, the synthesis of phosphorous fluorine-containing cooperative flame retardant compound:
By miscellaneous to carbon-to-nitrogen double bon intermediate and 0.91g (4.2mmol) the 9,10-dihydro-9-oxy of 2g (2.1mmol) step 1 gained
-10-phospho hetero phenanthrene-10-oxide joins in the single port flask of 100mL, and with 20mLN, dinethylformamide dissolves,
React 10h at 55 DEG C, precipitate with methanol, then cyclic washing three times, obtain pale yellow powder shape solid after vacuum drying,
It is phosphorous fluorine-containing cooperative flame retardant compound.
The sign of described phosphorous fluorine-containing cooperative flame retardant compound as in figure 2 it is shown, wherein chemical shift 5.5ppm to 6.1ppm be with
The characteristic peak of the C-H that nitrogen is connected, 6.5ppm to 8.3ppm is the characteristic peak of C-H on N-H and phenyl ring, is connected with phosphorus in addition
Carbon there is chirality, therefore the phosphorus spectrum of Fig. 3 demonstrates two Chiral properties peaks, two kinds of fluorine in fluorine in Fig. 4 spectrum display compound
Characteristic peak, this explanation product be target compound.
Embodiment 2
Step 1, the synthesis of intermediate containing carbon-to-nitrogen double bon:
First, by the 2 of 2g (3.86mmol), double [4-(4-amino-benzene oxygen) phenyl] 1,1,1,3,3, the 3-HFC-236fa and 1.86 of 2-
Double (trifluoromethyl) benzaldehyde of g (7.68mmol) 3,5-joins in the single port flask of 100mL, dissolves with 20mL methanol,
At 65 DEG C, stirring reaction 6h, is spin-dried for solvent with Rotary Evaporators, obtains pale yellow powder shape solid, i.e. after vacuum drying
For the intermediate containing carbon-to-nitrogen double bon.
Step 2, the synthesis of phosphorous fluorine-containing cooperative flame retardant compound:
By miscellaneous to carbon-to-nitrogen double bon intermediate and 0.91g (4.2mmol) the 9,10-dihydro-9-oxy of 2g (2.1mmol) step 1 gained
-10-phospho hetero phenanthrene-10-oxide joins in the single port flask of 100mL, and with 20mLN, dinethylformamide dissolves,
React 8h at 45 DEG C, precipitate with methanol, then cyclic washing three times, obtain pale yellow powder shape solid after vacuum drying,
It is described phosphorous fluorine-containing cooperative flame retardant compound.
Embodiment 3
Step 1, the synthesis of intermediate containing carbon-to-nitrogen double bon:
First, by the 4 of 2g (10.08mmol), 4'-MDA and 4.88g (20.16mol) 3, the double (fluoroform of 5-
Base) benzaldehyde joins in the single port flask of 100mL, dissolves with 20mL methanol, and stirring reaction 8h at 55 DEG C, with rotation
Turn evaporimeter to be spin-dried for by solvent, obtain pale yellow powder shape solid after vacuum drying, be the intermediate containing carbon-to-nitrogen double bon.
Step 2, the synthesis of phosphorous fluorine-containing cooperative flame retardant compound:
By carbon-to-nitrogen double bon intermediate and 1.34g (6.19mmol) the 9,10-dihydro-9-oxy of 2g (3.10mmol) step 1 gained
Miscellaneous-10-phospho hetero phenanthrene-10-oxide joins in the single port flask of 100mL, dissolves with 20mL DMF,
React 10h at 55 DEG C, precipitate with methanol, then cyclic washing three times, obtain pale yellow powder shape solid after vacuum drying,
It is described phosphorous fluorine-containing cooperative flame retardant compound.
Embodiment 4
Step 1, the synthesis of intermediate containing carbon-to-nitrogen double bon:
First, by the 4 of 2g (10.08mmol), 4'-MDA and 4.88g (20.16mol) 3, the double (fluoroform of 5-
Base) benzaldehyde joins in the single port flask of 100mL, dissolves with 20mL methanol, and stirring reaction 6h at 65 DEG C, with rotation
Turn evaporimeter to be spin-dried for by solvent, obtain pale yellow powder shape solid after vacuum drying, be the intermediate containing carbon-to-nitrogen double bon.
Step 2, the synthesis of phosphorous fluorine-containing cooperative flame retardant compound:
By carbon-to-nitrogen double bon intermediate and 1.34g (6.19mmol) the 9,10-dihydro-9-oxy of 2g (3.10mmol) step 1 gained
Miscellaneous-10-phospho hetero phenanthrene-10-oxide joins in the single port flask of 100mL, dissolves with 20mL DMF,
React 8h at 65 DEG C, precipitate with methanol, then cyclic washing three times, obtain pale yellow powder shape solid after vacuum drying,
It is described phosphorous fluorine-containing cooperative flame retardant compound.
Embodiment 5
Step 1, the synthesis of intermediate containing carbon-to-nitrogen double bon:
First, by the 2 of 2g (3.86mmol), double [4-(4-amino-benzene oxygen) phenyl] 1,1,1,3,3,3-HFC-236fa and the 2g of 2-
(8.26mmol) double (trifluoromethyl) benzaldehyde of 3,5-joins in the single port flask of 100mL, dissolves with 20mL methanol, in
At 55 DEG C, stirring reaction 8h, is spin-dried for solvent with Rotary Evaporators, obtains pale yellow powder shape solid, be after vacuum drying
Intermediate containing carbon-to-nitrogen double bon.
Step 2, phosphorous, the synthesis of fluorine cooperative flame retardant compound:
By carbon-to-nitrogen double bon intermediate and the miscellaneous-10-of 1g (4.63mmol) 9,10-dihydro-9-oxy of 2g (2.1mmol) step 1 gained
Phospho hetero phenanthrene-10-oxide joins in the single port flask of 100mL, and with 20mLN, dinethylformamide dissolves, 55 DEG C
Lower reaction 10h, precipitates with methanol, then cyclic washing three times, obtains pale yellow powder shape solid, be after vacuum drying
Described phosphorous fluorine-containing cooperative flame retardant compound.
Embodiment 6
Step 1, the synthesis of intermediate containing carbon-to-nitrogen double bon:
First, by the 4 of 2g (10.08mmol), 4'-MDA and 5.37g (22.18mol) 3, the double (fluoroform of 5-
Base) benzaldehyde joins in the single port flask of 100mL, dissolves with 20mL methanol, and stirring reaction 8h at 55 DEG C, with rotation
Turn evaporimeter to be spin-dried for by solvent, obtain pale yellow powder shape solid after vacuum drying, be the intermediate containing carbon-to-nitrogen double bon.
Step 2, the synthesis of described phosphorous fluorine-containing cooperative flame retardant compound:
By carbon-to-nitrogen double bon intermediate and 1.47g (6.81mmol) the 9,10-dihydro-9-oxy of 2g (3.10mmol) step 1 gained
Miscellaneous-10-phospho hetero phenanthrene-10-oxide joins in the single port flask of 100mL, dissolves with 20mL DMF,
React 10h at 55 DEG C, precipitate with methanol, then cyclic washing three times, obtain pale yellow powder shape solid after vacuum drying,
It is described phosphorous fluorine-containing cooperative flame retardant compound.
The above, only presently preferred embodiments of the present invention, also can make other equivalence changes and modify.
Claims (10)
1. a phosphorous fluorine-containing cooperative flame retardant compound, it is characterised in that its structural formula is as follows:
Wherein, R group is
The preparation method of a kind of phosphorous fluorine-containing cooperative flame retardant compound the most as claimed in claim 1, it is characterised in that include walking as follows
Rapid:
1) by diamino compounds and 3, double (trifluoromethyl) benzaldehyde of 5-reacts in the first solvent, and rotation is steamed, and is contained after drying
The intermediate of carbon-to-nitrogen double bon, its structural formula is as follows:
Wherein, R group is
2) by step 1) intermediate containing carbon-to-nitrogen double bon prepared and 9,10-dihydro-9-oxy miscellaneous-10-phospho hetero phenanthrene-10-oxide be the
Reacting in two solvents, product precipitant precipitates, then washs with precipitant, the most i.e. obtains phosphorous fluorine-containing cooperative flame retardant
Compound.
The preparation method of a kind of phosphorous fluorine-containing cooperative flame retardant compound the most as claimed in claim 2, it is characterised in that in step 1)
In, the one in described first solvent selected from methanol, ethanol, oxolane, dichloromethane, chloroform.
The preparation method of a kind of phosphorous fluorine-containing cooperative flame retardant compound the most as claimed in claim 2, it is characterised in that in step 1)
In, the proportioning of described diamino compounds and the first solvent is 1g: (1～20) mL, wherein, diamino compounds is with matter
Amount calculates, and the first solvent is in terms of volume.
The preparation method of a kind of phosphorous fluorine-containing cooperative flame retardant compound the most as claimed in claim 2, it is characterised in that in step 1)
In, the condition of described reaction is to react 2～10h at 25～90 DEG C.
The preparation method of a kind of phosphorous fluorine-containing cooperative flame retardant compound the most as claimed in claim 2, it is characterised in that in step 1)
In, described diamino compounds and 3, the mol ratio of double (trifluoromethyl) benzaldehyde of 5-is 1: (2～3)；Described being dried can use
Vacuum drying.
The preparation method of a kind of phosphorous fluorine-containing cooperative flame retardant compound the most as claimed in claim 2, it is characterised in that in step 2)
In, the described mol ratio containing carbon-to-nitrogen double bon intermediate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1: (2～3).
The preparation method of a kind of phosphorous fluorine-containing cooperative flame retardant compound the most as claimed in claim 2, it is characterised in that in step 2)
In, described second solvent is in DMF, dimethyl sulfoxide, ethyl acetate, dichloromethane, chloroform
A kind of.
The preparation method of a kind of phosphorous fluorine-containing cooperative flame retardant compound the most as claimed in claim 2, it is characterised in that in step 2)
In, the described proportioning containing carbon-to-nitrogen double bon intermediate and the second solvent is 1g: (1～20) mL, wherein, containing in carbon-to-nitrogen double bon
Mesosome is calculated by mass, and the second solvent is in terms of volume；The condition of described reaction can react 8～12h at 25～90 DEG C.
The preparation method of a kind of phosphorous fluorine-containing cooperative flame retardant compound the most as claimed in claim 2, it is characterised in that in step 2)
In, described precipitant one in methanol, ethanol, normal hexane；Washable 3 times of described washing；Described being dried can use
Vacuum drying.
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| CN201610053910.5A CN105732715A (en) | 2016-01-27 | 2016-01-27 | Phosphorus-containing fluorine-containing synergic flame-retardant compound and preparation method thereof |
| PCT/CN2017/070971 WO2017128960A1 (en) | 2016-01-27 | 2017-01-12 | Phosphorus-containing fluorine-containing synergistic flame-retardant compound and preparation method therefor |
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